EP4692170A1

EP4692170A1 - Organopolysiloxane compound, composition containing same, and cured product thereof

Info

Publication number: EP4692170A1
Application number: EP24815057.5A
Authority: EP
Inventors: Takayuki Suzuki
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2023-06-01
Filing date: 2024-04-25
Publication date: 2026-02-11
Also published as: WO2024247572A1; CN121263465A; JPWO2024247572A1

Abstract

Provided is a highly reactive organopolysiloxane compound and a composition containing the same. The organopolysiloxane compound is represented by formula (1) wherein, in formula (1), W is a bivalent organopolysiloxane residue, L represents an alkylene group having 2 to 12 carbon atoms, each X_i independently represents at least one group selected from an alkyl group having 1 to 18 carbon atoms and a group represented by formula (3) wherein, in the formula (3), M, Ls, and X_is are as defined above, each Z independently represents an oxygen atom or the like, b is a number of 2 to 20, M represents a polyvalent organic group having (b+1) valency, M represents a polyvalent organic group having (b+1) valency, i is a number of 1 to 5 provided that i begins with 1, and a_i is a number of 0 to b provided that b is a number of 1 to 20, with the proviso that at least one X_i in the formula (1) is a group represented by the formula (3) in which b - a₁ is a number greater than 1.

Description

Technical Field

The present invention relates to an organopolysiloxane compound having acryloyl groups that are radically polymerizable, a composition containing the same, and a cured product thereof.

Background Art

In recent years, as energy saving and reduction in the number of steps are demanded more than ever, a light-curable resin that is curable at room temperature in a short period of time has gained attention and such resin generally employs a radically polymerizable acrylic compound as an ingredient. This light-curable resin is used in, for example, paints, coatings, or inks, where high water repellency, antifouling properties, lubricity, or similar characteristics are sometimes required.
A method known for imparting high water repellency, antifouling properties, lubricity, or similar characteristics to a light-curable resin includes the formulation of a (meth)acryloyl group-containing organopolysiloxane for copolymerization (Patent document 1).
However, many (meth)acryloyl group-containing organopolysiloxanes exhibit low reactivity, often leading to challenges such as the bleeding of unreacted organopolysiloxanes from the cured resin over time (Patent document 2).
In view of this, an organopolysiloxane compound capable of addressing these issues has been highly sought after.

Prior Art Documents

Patent documents

Patent document 1: JP-A-2022-138932
Patent document 2: JP-A-2005-36018

Summary of Invention

Technical Problem

It is therefore an object of the present invention to provide a radically polymerizable organopolysiloxane compound that is highly reactive, a composition containing the same, and a cured product thereof.

Solution to Problem

The inventor of the present invention has diligently conducted a series of studies to solve the above problems and has found that a specific type of organopolysiloxane compound having acryloyl groups can achieve the above object, thus completing the present invention.
That is, the present invention is directed to those as set forth below.

<1> An organopolysiloxane compound represented by formula (1) defined as
- wherein, in the formula (1), W is a group represented by formula (2) defined as wherein, in the formula (2), each R¹ independently represents a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and n is a number of 0 to 1,000, and
- wherein each L independently represents an alkylene group having 2 to 12 carbon atoms, each X_i independently represents at least one group selected from an alkyl group having 1 to 18 carbon atoms (said alkyl group optionally containing at least one selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group) and a group represented by formula (3) defined as wherein, in the formula (3), Ws, Ls, and X_is are as defined above, each Z independently represents an oxygen atom, a sulfur atom, or a group represented by NR² where R² in the NR² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M represents a polyvalent organic group having (b+1) valency, i is a number of 1 to 30 provided that i begins with 1, and a_i is a number of 0 to b, where b is a number of 1 to 20,
- with the proviso that at least one X_i in the formula (1) is a group represented by the formula (3) in which b - a₁ is a number greater than 1.
<2> The organopolysiloxane compound according to <1>, wherein all X_is are each a group represented by the formula (3).
<3> The organopolysiloxane compound according to <1> or <2>, wherein b is a number of 1 to 5.
<4> A composition comprising the organopolysiloxane compound according to any one of <1> to <3>.
<5> The composition according to <4>, further comprising at least one acrylic compound that is not a compound of said organopolysiloxane compound.
<6> The composition according to <5>, wherein the acrylic compound is a polyvalent acrylic monomer having a valence of (b+1).
<7> A cured product of the composition according to any one of <4> to <6>.

Advantageous Effects of Invention

The organopolysiloxane compound of the present invention is highly light-curable and reactive, and is less likely to cause bleeding when it is formulated in a light-curable resin composition and copolymerized therewith. Moreover, the organopolysiloxane compound of the present invention cures with a lesser amount of energy, enabling energy saving and a reduction in the number of steps for producing a cured product thereof.
The present invention is suitable for, for example, paints, coating agents, and inks.

Brief Description of Drawings

FIG. 1 is a ¹H-NMR spectrum chart of an organopolysiloxane compound synthesized in Working Example 1.
FIG. 2 is a GPC chart of an organopolysiloxane compound synthesized in Working Example 1.

Description of Embodiments

The present invention will be described hereunder in greater detail.

[Organopolysiloxane compound]

The organopolysiloxane compound of the present invention is represented by formula (1) defined below and has an acryloyl group per molecule, which allows the compound to be readily reacted with a radically polymerizable compound.
In the formula (1), W is a group (a bivalent organopolysiloxane-containing group) represented by formula (2) defined as
In formula (2), each R¹ independently represents a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and is preferably a methyl group or a phenyl group, and is more preferably a methyl group. n is a number of 0 to 1,000, preferably a number of 3 to 500, and more preferably a number of 5 to 200.
Examples of groups represented by the above formula (2) include, but are not particularly limited to, groups represented by formulae (4) to (7) defined as:
In the formula (1), L represents an alkylene group having 2 to 12 carbon atoms, preferably an alkylene group having 3 to 8 carbon atoms, and more preferably an alkylene group having 3 to 4 carbon atoms.
In the formula (1), each X_i independently represents a group selected from an alkyl group having 1 to 18 carbon atoms (this alkyl group may contain at least one selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group) and a group represented by formula (3) defined below, and X_i preferably represents a group defined by formula (3):
In the formula (3), Ws, Ls, and X_is are as exemplified for the ones defined in the formula (1). Each Z independently represents an oxygen atom, a sulfur atom, or a group represented by NR², and is preferably an oxygen atom. R² in the NR² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and is preferably a hydrogen atom. M represents a polyvalent organic group having (b+1) valency and is preferably a bi- to hexa-valent polyvalent group, and more preferably is a bi- to hexa-valent aliphatic hydrocarbon group optionally having an ether bond and a hydroxyl group. i is a number of 1 to 30, preferably of 1 to 20, and more preferably of 1 to 10, provided that i begins with 1. a_i is an integer of 0 to b and a₁₀ is preferably 0. b is a number of 1 to 20, preferably of 1 to 5.
Examples of the polyvalent organic group M defined above include, but are not particularly limited to, the groups shown below.
Examples of X_i defined above include, but are not particularly limited to, the groups as defined below:
It is preferred that the organopolysiloxane compound represented by the above formula (1) have a number average molecular weight (Mn) of 500 to 50,000, more preferably of 1,000 to 30,000, and particularly preferably of 2,000 to 20,000, and the "i" in the formula (3) is a number of 1 to 30 that is determined to satisfy this number average molecular weight (Mn).
The term "number average molecular weight" as used herein refers to a number average molecular weight determined by the GPC (gel permeation chromatography) using polystyrene as a reference material and measured under the conditions shown below.

[Measurement Conditions]

Developing Solvent:	Tetrahydrofuran
Flow Rate:	0.6 mL/min
Detector:	Refractive Index Detector (RI)
Column:	TSK Guard Column Super H-H
	TSKgel Super HM-N (6.0 mm I.D. × 15 cm × 1)
	TSKgel Super H2500 (6.0 mm I.D. × 15 cm × 1) (All manufactured by Tosoh Corporation)
Column Temperature:	40°C
Sample Injection Volume:	50 µL (0.3 wt% tetrahydrofuran solution)

[Method for producing organopolysiloxane compound]

The organopolysiloxane compound of the present invention represented by the above formula (1) may be produced by, for example, a method explained below.
Specifically, the Michael addition reaction, as depicted by the reaction formula (A) below, may be used to react an organopolysiloxane, having a primary or secondary amino group at both ends, with a bi- or higher functional acrylic compound to thereby produce the compound.
In the reaction formula (A) above, examples of W, L, Z, M, b, and X_i include those as defined in the formula (1). Each X independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms (this alkyl group may contain at least one selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group), where X_i in the reaction product reduces to a group represented by the formula (3) through the reaction of two equivalents of acrylic groups per -NH₂ when X is a hydrogen atom; that is, when the organopolysiloxane contains a primary amino group.
Examples of the bi- or higher functional acrylic compound include 2-functional acrylic monomers such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and tripropylene glycol diacrylate; 3-functional acrylic monomers such as trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerol triacrylate, and pentaerythritol triacrylate; 4-functional acrylic monomers such as pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and ditrimethylolpropane tetraacrylate; 5-functional acrylic monomers such as dipentaerythritol pentaacrylate; 6-functional acrylic monomers such as dipentaerythritol hexaacrylate; and oligomer acrylic compounds such as urethane acrylate, polyester acrylate, and epoxy acrylate. It is preferred in terms of reactivity of the organopolysiloxane represented by the above formula (1) and obtained by the Michael addition reaction that the bi- or higher functional acrylic compound be a 2 to 6 functional acrylic monomer.
It is preferable to conduct the reaction by adjusting the formulation to include one or more equivalents of the bi- or higher functional acrylic compound for each -NH- group in the organopolysiloxane. In this case, the reaction product is an organopolysiloxane compound, represented by the formula (1) that is favorably light-curable and reactive.
The above reaction may proceed without using any catalyst by only mixing an organopolysiloxane having an amino group with a bi- or higher functional acrylic compound and heating the mixture to produce the organopolysiloxane compound represented by the formula (1). However, an acid catalyst or a base catalyst may be added thereinto if necessary.
Examples of the acid catalyst include AlCl₃ and MgCl₂.
Examples of the base catalyst include non-nucleophilic tertiary amines (such as N,N,N',N'-tetramethyl-1,8-diaminonaphthalene and 1,8-diazabicyclo[5.4.0]undec-7-ene).
These catalysts may be used alone or two or more of them may be used in combination.
The above reaction may be performed at any temperature which is not particularly limited, but it is preferable for the purposes of preventing the polymerization of acrylic groups and promoting the reaction that the temperature be 20 to 100°C, more preferably 50 to 80°C.
The above reaction may be performed for any duration which is not particularly limited, but it is preferred that the duration be 3 to 24 hours, more preferably 6 to 18 hours.
It is preferred that a solvent be added to perform the above reaction. The added solvent makes it easy for the organopolysiloxane having an amino group and the bi- or higher functional acrylic compound to be compatible with each other, and is preferable because it efficiently allows promotion of the Michael addition reaction. It is preferred that the solvent have no groups capable of reacting with an amino group or an acrylic group, and examples thereof include hydrocarbons (such as toluene, xylene, n-hexane, and cyclohexane) and ethers (such as diethyl ether, tetrahydrofuran, and 1,4-dioxane). Any one kind of these solvents may be used alone or two or more of them may be used in combination.
Further, a polymerization inhibitor may also be added if necessary to perform the above reaction. Examples of such polymerization inhibitor may include those that have been conventionally used for acrylic compounds. Specific examples of the polymerization inhibitor include phenolic polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 2-tert-butylhydroquinone, 4-methoxyphenol, and 2,6-di-tert-butyl-p-cresol. Any one kind of these polymerization inhibitors may be used alone, or two or more kinds thereof may be used in combination. There are no particular limitations on the amount of the polymerization inhibitor; it is preferred that the polymerization inhibitor be used in an amount of 5 to 1,000 ppm, more preferably 20 to 500 ppm, with respect to the mass of the compound to be obtained.

[Composition containing organopolysiloxane compound]

The composition of the present invention contains the organopolysiloxane compound of the present invention as described above. The composition of the present invention may contain not only the above-described organopolysiloxane compound of the present invention but also at least one acrylic compound that is not an organopolysiloxane compound of the present invention.
The organopolysiloxane compound of the present invention is highly light-curable and reactive, which allows a composition containing the compound to be cured with a lesser amount of energy.
Further, the reaction for producing the organopolysiloxane compound potentially leaves an unreacted bi- or higher functional acrylic compound having a valence of (b+1) (e.g., a polyfunctional acrylic monomer) in the reaction product. This unreacted acrylic compound can be removed through, for example, solvent extraction, or directly utilized as a copolymerizing monomer for the composition of the present invention. That is, regarding the composition of the present invention, the reaction product obtained in the above-described method may be provided as a composition of the present invention containing an organopolysiloxane compound represented by the formula (1) and a bi- or higher functional acrylic compound having a valence of (b+1). In this case, examples of the bi- or higher functional acrylic compound having a valence of (b+1) contained in the composition of the present invention include a variety of acrylic compounds listed as bi- or higher functional acrylic compounds each having a valence of (b+1) and shown in the above reaction formula (A), and it is preferred that the acrylic compound be a 2- to 6- functional acrylic monomer.
Further, the mixture of the organopolysiloxane compound represented by the formula (1) obtained in the above reaction and the unreacted bi- or higher functional acrylic compound having a valence of (b+1) may be purified by a conventional method and used therein to which at least one type of acrylic compound, preferably a polyvalent acrylic monomer having a valence of (b+1), more preferably a 2- to 6- functional acrylic monomer, may be separately added to prepare the composition of the present invention.
Furthermore, the mixture of the organopolysiloxane compound represented by the formula (1) obtained in the above reaction and the unreacted tri- or higher functional acrylic compound having a valence of (b+1) may be used directly or purified by a conventional method and used therein to which at least one type of acrylic compound, preferably a polyvalent acrylic monomer having a valence of (b+1), more preferably a 3- to 6- functional acrylic monomer, may be separately added to prepare the composition of the present invention.

[Cured product]

The composition according to the present invention may be cured to produce a cured product of the present invention. As to the curing, a conventional method may be used to radically polymerize the above composition by heat or light to promote the curing to produce the cured product.

Examples

The present invention will be described in detail hereunder with reference to working and comparative examples; the present invention shall not be limited to the following working examples. In the following examples, the number average molecular weight and dispersity (weight average molecular weight/number average molecular weight) are polystyrene-equivalent values determined by GPC (gel permeation chromatography) measurement using tetrahydrofuran as a developing solvent under the conditions shown below.

[Measurement Conditions]

[Working Example 1]

70.5g of an organopolysiloxane having an amino group at both ends and represented by formula (8-1) shown below, 31.4 g of 1,6-hexanediol diacrylate, 67.9 g of toluene, and 0.031 g of 2,6-di-tert-butyl-p-cresol were put into a reaction container and stirred with each other at 70°C for 20 hours to prepare a mixed solution. Then, the toluene was distilled off under reduced pressure from the mixed solution to yield a liquid product. 86.0 g of methanol was added to the resultant liquid product to perform washing, followed by performing liquid phase separation to recover the organopolysiloxane phase. The same washing process was repeated three times in total, and the residual methanol was subsequently distilled off under reduced pressure to yield 46.3g of a liquid product (FIGs. 1 and 2).

[Table 1]

Number average molecular weight and dispersity of resultant liquid product
Number average molecular weight	Dispersity
10,680	1.87

[Table 2]

Chemical shift of ¹H-NMR spectrum of resultant liquid product (Measurement device: AVANCE 400 manufactured by Bruker Corporation; Solvent: CDCl₃)
Shifts (ppm; TMS reference)		Integral ratio (H)
-0.16 to 0.26	-Si-CH₃	372
0.45	-Si-CH₂ -CH₂-CH₂-N<	4
1.29 to 1.51	-(C=O)-O-CH₂-CH₂ -CH₂- -Si-CH₂-CH₂ -CH₂-N<	20
1.52 to 1.76	-(C=O)-O-CH₂-CH₂-CH₂ -	16
2.33 to 2.51	-Si-CH₂-CH₂-CH₂ -N< >N-CH₂ -CH₂-(C=O)-O-	12
2.77	>N-CH₂-CH₂ -(C=O)-O-	8
4.01 to 4.10	-CH₂-CH₂-(C=O)-O-CH₂ -	10
4.12 to 4.19	CH ₂=CH-(C=O)-O-CH₂ -	6
5.81	CH ₂=CH-(C=O)-O-	3
6.12	CH₂=CH-(C=O)-O-	3
6.40	CH ₂=CH-(C=O)-O-	3

The above results demonstrate that the resultant liquid product was an organopolysiloxane represented by formula (1-1) shown below.

X_i :
M : -CH₂CH₂CH₂CH₂CH₂CH₂-

_i

[Working Example 2]

57.8 g of an organopolysiloxane having an amino group at both ends and represented by formula (8-2) shown below, 38.2 g of tripropylene glycol diacrylate, 64.0 g of toluene, and 0.029 g of 2,6-di-tert-butyl-p-cresol were put into a reaction container and stirred with each other at 70°C for 20 hours to prepare a mixed solution. Then, the toluene was distilled off under reduced pressure from the mixed solution to yield 91.7 g of a liquid product.

[Table 3]

GPC measurement results of resultant liquid product
GPC peak	Number average molecular weight	Dispersity	GPC area %	Determined compound
1	4,410	1.64	56.6	Formula (1-2) specified below
2	320	1.04	43.4	Tripropylene glycol diacrylate

[Table 4]

Chemical shift of ¹H-NMR spectrum of resultant liquid product (Measurement device: AVANCE 400 manufactured by Bruker Corporation; Solvent: CDCl₃)
Shifts (ppm; TMS reference)		Integral ratio (H)
-0.17 to 0.25	-Si-CH₃	132
0.45	-Si-CH₂ -CH₂-CH₂-N<	4
1.05 to 1.32	-O-CH₂-CH(CH₃ )-O-	83
1.42	-Si-CH₂-CH₂ -CH₂-N<	4
2.33 to 2.49	-Si-CH₂-CH₂-CH₂ -N< >N-CH₂ -CH₂-(C=O)-O-	12
2.76	>N-CH₂-CH₂ -(C=O)-O-	8
3.26 to 3.65	-(C=O)-O-CH₂-CH(CH₃)-O-CH₂ -CH (CH₃)-O-CH₂ -CH(CH₃)-O-(C=O)-	50
3.65 to 3.88	-(C=O)-O-CH ₂-CH(CH₃)-O-	12
3.97 to 4.18	-(C=O)-O-CH ₂-CH(CH₃)-O-	12
4.95 to 5.21	-O-CH₂-CH(CH₃)-O-(C=O)-	12
5.81	CH ₂=CH-(C=O)-O-	13
6.12	CH₂=CH-(C=O)-O-	13
6.40	CH ₂=CH-(C=O)-O-	13

The above results demonstrate that the resultant liquid product was a mixture of an organopolysiloxane represented by formula (1-2) shown below and tripropylene glycol diacrylate.

X_i :
M :

_i

[Working Example 3]

52.1 g of an organopolysiloxane having an amino group at both ends and represented by the above formula (8-2), 35.0 g of trimethylolpropane triacrylate, 58.1 g of toluene, and 0.026 g of 2,6-di-tert-butyl-p-cresol were put into a reaction container and stirred with each other at 70°C for 20 hours to prepare a mixed solution. Then, the toluene was distilled off under reduced pressure from the mixed solution to yield 80.6 g of a liquid product.

[Table 5]

GPC measurement results of resultant liquid product
GPC peak	Number average molecular weight	Dispersity	GPC area %	Determined compound
1	6,400	2.95	52.6	Formula (1-3) specified below
2	330	1.21	47.4	Trimethylolpropane triacrylate

[Table 6]

Chemical shift of ¹H-NMR spectrum of resultant liquid product (Measurement device: AVANCE 400 manufactured by Bruker Corporation; Solvent: CDCl₃)
Shifts (ppm; TMS reference)		Integral ratio (H)
-0.17 to 0.25	-Si-CH₃	132
0.45	-Si-CH₂ -CH₂-CH₂-N<	4
0.92	-CH₂-CH₃	27
1.42	-Si-CH₂-CH₂ -CH₂-N<	4
1.54	-CH₂ -CH₃	18
2.33 to 2.49	-Si-CH₂-CH₂-CH₂ -N< >N-CH₂ -CH₂-(C=O)-O-	12
2.76	>N-CH₂-CH₂ -(C=O)-O-	8
3.95 to 4.22	-(C=O)-O-CH₂ -	54
5.85	CH ₂=CH-(C=O)-O-	20
6.11	CH₂=CH-(C=O)-O-	20
6.40	CH ₂=CH-(C=O)-O-	20

The above results demonstrate that the resultant liquid product was a mixture of an organopolysiloxane represented by formula (1-3) shown below and trimethylolpropane triacrylate.

X_i :
M :

_i

[Working example 4]

3.98 g of an organopolysiloxane having an amino group at both ends and represented by the above formula (8-2), 11.6 g of dipentaerythritol hexaacrylate, 10.4 g of toluene, and 0.005 g of 2,6-di-tert-butyl-p-cresol were put into a reaction container and stirred with each other at 70°C for 20 hours to prepare a mixed solution. Then, the toluene was distilled off under reduced pressure from the mixed solution to yield 12.2 g of a liquid product.

[Table 7]

GPC measurement results of resultant liquid product
GPC peak	Number average molecular weight	Dispersity	GPC area %	Determined compound
1	6,330	2.11	39.2	Formula (1-4) specified below
2	680	1.21	60.8	Dipentaerythritol hexaacrylate

[Table 8]

Chemical shift of ¹H-NMR spectrum of resultant liquid product (Measurement device: AVANCE 400 manufactured by Bruker Corporation; Solvent: CDCl₃)
Shifts (ppm; TMS reference)		Integral ratio (H)
-0.15 to 0.24	-Si-CH₃	132
0.47	-Si-CH₂ -CH₂-CH₂-N<	4
1.41	-Si-CH₂-CH₂ -CH₂-N<	4
2.33 to 2.48	-Si-CH₂-CH₂-CH₂ -N< >N-CH₂ -CH₂-(C=O)-O-	12
2.75	>N-CH₂-CH₂ -(C=O)-O-	8
3.34 to 3.51	-CH₂ -O-CH₂ -	40
4.04 to 4.33	-(C=O)-O-CH₂ -	104
5.85	CH ₂=CH-(C=O)-O-	44
6.09	CH₂=CH-(C=O)-O-	44
6.39	CH₂ =CH-(C=O)-O-	44

The above results demonstrate that the resultant liquid product was a mixture of an organopolysiloxane represented by formula (1-4) shown below and dipentaerythritol hexaacrylate.

x_i :
M :

_i

[Comparative Example 1]

A bifunctional acrylic-modified organopolysiloxane represented by formula (9) defined as

[Comparative Example 2]

A polyfunctional acrylic-modified organopolysiloxane represented by formula (10) defined as

[Comparative Example 3]

1,6-Hexanediol diacrylate

[Comparative Example 4]

Tripropylene glycol diacrylate

[Comparative Example 5]

Trimethylolpropane triacrylate

[Comparative Example 6]

Dipentaerythritol hexaacrylate

[Evaluation of UV Curability]

0.020 g of a photopolymerization initiator-Omnirad 1173 manufactured by IGM Resins-was added to 10 g of each of the compositions of the working examples or the compounds of the comparative examples to prepare a liquid composition. The gelation time (the time at which the storage modulus (G') = loss modulus (G")) of the liquid composition was measured under the following conditions using a viscoelasticity measuring device (DHR2 (Discovery Hybrid Rheometer) manufactured by TA Instruments) to evaluate UV curability. The results are as shown in Table 9.

[Gelation Time Measurement Conditions]

UV Light Source: (manufactured by Excelitas Technologies Corp.)	OmniCure SERIES 2000
UV Illuminance:	10 mW/cm²
Viscoelasticity Measurement Device: (manufactured by TA Instruments)	DHR2 (Discovery Hybrid Rheometer)
Measurement Mode:	Compression
Initial Torque:	10.0 µN·m
Strain:	10.0%
Frequency:	25.0 Hz
Sample Film Thickness:	200 µm

[Table 9]

	Working Example 1	Working Example 2	Working Example 3	Working Example 4
Gelation time (seconds)	23.6	14.1	13.7	29.4

	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Gelation time (seconds)	77.5	78.8	37.5	33.8	28.9	51.7

[Evaluation of bleeding]

10 g of trimethylolpropane triacrylate and 0.1 g of photopolymerization initiator-Omnirad 1173 manufactured by IGM Resins-were added to 0.5 g of each of the compositions of the working examples or the compounds of the comparative examples to prepare a liquid composition, and each solution was applied to a polycarbonate substrate using a No. 4 bar coater. An ultraviolet curing device (MUVBA manufactured by AITEC SYSTEM Co., Ltd.) was used to irradiate the coated film with UV light of 365 nm wavelength and 140 mW/cm² intensity for two seconds under a nitrogen atmosphere to cure the film, and the presence or absence of bleeding was then evaluated through tactile assessment. The results are as shown in Table 10.

[Table 10]

	Working Example 1	Working Example 2	Working Example 3	Working Example 4	Comparative Example 1	Comparative Example 2
Presence or absence of bleeding	Absent	Absent	Absent	Absent	Present	Present

The results in Table 9 show that the organopolysiloxane compounds of the present invention reach their gelation time points earlier than those of the conventional acrylic-modified organopolysiloxanes, demonstrating more enhanced UV curability of the compounds. Furthermore, it was surprisingly found that the organopolysiloxane compound of the present invention, in which an organopolysiloxane having a primary amino group is subjected to Michael addition to a polyfunctional acrylic compound, has higher UV curability than the polyfunctional acrylic compound used as the raw material. Furthermore, the results in Table 10 show that the organopolysiloxane compounds of the present invention have high UV curability, and therefore demonstrate that they are less likely to bleed.
The organopolysiloxane compound of the present invention is therefore useful as, for example, an ingredient to be blended into, for example, UV-curable resin compositions, as a UV-curable silicone elastomer, or as a coating agent.

Claims

An organopolysiloxane compound represented by formula (1) defined as
wherein, in the formula (1), W is a group represented by formula (2) defined as wherein, in the formula (2), each R¹ independently represents a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and n is a number of 0 to 1,000, and

wherein each L independently represents an alkylene group having 2 to 12 carbon atoms, each X_i independently represents at least one group selected from an alkyl group having 1 to 18 carbon atoms (said alkyl group optionally containing at least one selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group) and a group represented by formula (3) defined as wherein, in the formula (3), Ws, Ls, and X_is are as defined above, each Z independently represents an oxygen atom, a sulfur atom, or a group represented by NR² where R² in the NR² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M represents a polyvalent organic group having (b+1) valency, i is a number of 1 to 30 provided that i begins with 1, and a_i is a number of 0 to b, where b is a number of 1 to 20,

with the proviso that at least one X_i in the formula (1) is a group represented by the formula (3) in which b - a₁ is a number greater than 1.
The organopolysiloxane compound according to claim 1, wherein all X_is are each a group represented by the formula (3).
The organopolysiloxane compound according to claim 2, wherein b is a number of 1 to 5.
A composition comprising the organopolysiloxane compound according to claim 1.
The composition according to claim 4, further comprising at least one acrylic compound that is not a compound of said organopolysiloxane compound.
The composition according to claim 5, wherein the acrylic compound is a polyvalent acrylic monomer having a valence of (b+1).
A cured product of the composition according to claim 4.